Calculating Change in Enthalpy of Constant Volume Process

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Discussion Overview

The discussion revolves around calculating the change in specific enthalpy during a constant volume process involving a gas. Participants explore the appropriateness of using the specific heat capacity at constant pressure (Cp) in this context, considering the implications of the process being isochoric (constant volume) and the relationship between enthalpy, temperature, and pressure.

Discussion Character

  • Technical explanation, Conceptual clarification, Debate/contested

Main Points Raised

  • One participant questions the validity of using Cp, which is defined for constant pressure processes, in the calculation of change in enthalpy for a constant volume process.
  • Another participant clarifies that the gas is being heated, not compressed, which is relevant to the discussion of enthalpy changes.
  • A different participant suggests reviewing the formal definition of enthalpy, noting that the enthalpy change can still be relevant in an isochoric process due to external pressure changes requiring energy input.
  • One participant emphasizes that enthalpy is a property of the gas dependent on temperature and pressure, and not solely on the process characteristics, arguing that enthalpy changes can be determined from equilibrium states regardless of the process type.
  • The same participant explains that Cp is defined as the partial derivative of enthalpy with respect to temperature, linking it to experimental measurements conducted at constant pressure.

Areas of Agreement / Disagreement

Participants express differing views on the appropriateness of using Cp in a constant volume process, with some supporting its use based on the properties of enthalpy and others questioning it. The discussion remains unresolved regarding the application of Cp in this specific context.

Contextual Notes

Participants highlight the importance of understanding the definitions and relationships between enthalpy, temperature, and pressure, as well as the implications of the process being constant volume. There are unresolved assumptions regarding the applicability of Cp in this scenario.

Who May Find This Useful

This discussion may be useful for students and professionals in thermodynamics, particularly those interested in the properties of gases and the calculations related to enthalpy changes in various processes.

ajayguhan
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I was asked to find the change in specific enthalpy of constant volume process.

Mass of 10 kg of a gas is heated to a pressure of about 2 times the initial pressure. The initial temperature was 20°C.

The process is a reversible, non-flow, constant volume process.

I found out the final temperature which is 40°C

Change in enthalpy Δh=Cp*Δt

My question is, is it correct to use Cp which is defined for a constant pressure process in a constant volume process?

If it's correct then how it is correct?
 
Last edited:
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How can the gas be compressed if its volume is constant?

Chet
 
Sorry it's is heated not compressed.
 
You need to look at the formal definition of enthalpy on Wikipedia to understand.

At some point you will find the following equation:

c25908f7c6c63ac4b7422cd7d91b2c16.png


The left part is the definition of enthalpy. The first two terms of the right part are the internal energy dU and the third term is the work done.

The second term of the right part is the internal work done (which affects the internal energy and the enthalpy) and the third term could be seen as the total work done (I'm not sure it's the proper terminology).

The thing is that the pdV term is also included in the d(pV) term (= pdV + Vdp). This is why we end up with:

8e15be705c669a27bdd04c2882bf26bc.png


In an isochoric process, TdS is the internal energy because there is no internal work done, but dp is not equal to zero so the enthalpy is still higher than the internal energy.

The way to think of it is, even though there is no volume change, that change in exterior pressure to keep the volume constant requires some energy from an exterior source.
 
Last edited by a moderator:
ajayguhan said:
I was asked to find the change in specific enthalpy of constant volume process.

Mass of 10 kg of a gas is heated to a pressure of about 2 times the initial pressure. The initial temperature was 20°C.

The process is a reversible, non-flow, constant volume process.

I found out the final temperature which is 40°C

Change in enthalpy Δh=Cp*Δt

My question is, is it correct to use Cp which is defined for a constant pressure process in a constant volume process?

If it's correct then how it is correct?
There is an important point that, in my opinion, is always omitted, or at least, under-emphasized in thermodynamics texts. Enthalpy represents a physical property of the particular gas, and is not intrinsically related to the characteristics of any particular process. It is a function only of the temperature and pressure of the gas. So, for example, if you tell me the temperature and pressure of a particular gas in two different equilibrium states, I can tell you the change in enthalpy (per unit mass) between these states. All I need to do this is a table of enthalpy (per unit mass) as a function of temperature and pressure. For an ideal gas, things are even simpler. At low pressures, where ideal gas behavior prevails, the enthalpy is a function only of temperature.

So where does this constant pressure business come into play? Well, this is how we experimentally measure the enthalpy values that go into the table (once and for all). By doing an experiment at constant pressure, the change in enthalpy between equilibrium state A and equilibrium state B is equal to the amount of heat we have to add in the process to get from state A to state B. But, once these measurements have been performed, they never have to be performed again.

What we call the heat capacity Cp is simply equal to the partial derivative of the enthalpy with respect to temperature.

Hope this helps.

Chet
 

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